CN108671849A - A kind of anionic gemini surfactant and preparation method thereof - Google Patents
A kind of anionic gemini surfactant and preparation method thereof Download PDFInfo
- Publication number
- CN108671849A CN108671849A CN201810438784.4A CN201810438784A CN108671849A CN 108671849 A CN108671849 A CN 108671849A CN 201810438784 A CN201810438784 A CN 201810438784A CN 108671849 A CN108671849 A CN 108671849A
- Authority
- CN
- China
- Prior art keywords
- tartaric acid
- present
- preparation
- anionic
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 0 C*NC(**)=O Chemical compound C*NC(**)=O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/14—Derivatives of phosphoric acid
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of anionic gemini surfactants, using tartaric acid and fatty amine as raw material, first synthesize tartaric acid amide, anionic group is connected by etherification reaction, substitution reaction or esterification etc. on two secondary alcohol of tartaric acid amide again, synthesize tartaric acid amide anion type Gemini surface active agent, the ability that the Gemini surface active agent reduces aqueous solution surface tension is stronger, and critical micelle concentration value is 10‑5The order of magnitude.The surfactant is raw materials used to be easy to get, and tartaric acid Nantural non-toxic is degradable, and synthesis technology is simple, at low cost, and product is because containing amide group, using being readily biodegradable after discharge.
Description
Technical field
The present invention relates to technical field of surfactant more particularly to a kind of anionic gemini surfactants and its system
Preparation Method.
Background technology
Gemini surface active agent is the novel surfactant for having double-hydrophilic-parents' oil base structure, by hydrophilic radical
Type, Gemini surface active agent can be divided into anionic, four class of cationic, nonionic and amphoteric.Because of its uniqueness
Structure, Gemini surface active agent have lower critical micelle concentration and Krafft points, higher surface-active, excellent water
Dissolubility and salt resistant character are the surfactants of new generation of great application prospect.
In the past 20 years, more deep in terms of the synthesis of Gemini surface active agent and performance study both at home and abroad, synthesize perhaps
The Gemini surface active agent of multiple types.In view of factors such as environmental protection, Products Eco safeties, the Gemini surface active agent synthesized in recent years
Mainly based on glycosyl class, decomposable asymmetric choice net and degradable.Wherein, the molecule knot of decomposable asymmetric choice net and degradable Gemini surface active agent
Acetal radical, ester group or amide group are mainly contained in structure, the characteristics of these groups is stable under certain condition, in other condition
Under it is easily decomposes or degradation, introduce in the molecular structure such group be develop biodegradation type surfactant a way
Diameter.
However, although the type of developed Gemini surface active agent is more, the property of existing Gemini surface active agent
Valence is than to be improved.
Invention content
The purpose of the present invention is to provide a kind of amide-containing anionic gemini surfactants and preparation method thereof, carry
The performance of high Gemini surface active agent, and non-toxic or low-toxic degradable material can be rapidly decomposed into after using discharge.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
The present invention provides a kind of anionic gemini surfactants, have structure shown in Formulas I：
N=5~29 in Formulas I, R are-SO3M、-CH2CH2CH2SO3M、-SO3OM、-COOM、-CH2COOM or-PO3M2, M is
Na+、K+Or NH4 +。
Preferably, the anionic gemini surfactant includes
The present invention provides the preparation method of anionic gemini surfactant described in above-mentioned technical proposal, including it is following
Step：
(1) tartaric acid, thionyl chloride and solvent are mixed, carries out esterification, obtains diester tartaric acid used；
(2) the diester tartaric acid used, solvent and fatty amine are mixed, carries out amidation process, obtains tartaric acid amide；
(3) the tartaric acid amide is placed in reactor, under protective atmosphere, anion is added dropwise in ice-water bath
Change reagent, is reacted directly or under the action of catalyst, then with alkali neutralization, obtain tartaric acid amide anion type Shuangzi surface
Activating agent.
Preferably, the molar ratio of thionyl chloride and tartaric acid is 2~2.5 in the step (1).
Preferably, step (1) mesotartaric acid is levotartaric acid.
Preferably, the solvent in the step (1) and step (2) is methanol or ethyl alcohol.
Preferably, in the step (1) temperature of esterification be solvent boiling point, time of esterification is 4~
16h。
Preferably, the temperature of amidation process is the reflux temperature of solvent, the time of amidation process in the step (2)
For 6~12h.
Preferably, the catalyst of the step (3) is sodium hydride or sodium, and alkali is sodium hydroxide or potassium hydroxide.
Preferably, anionic reagent is propane sultone, chlorosulfonic acid, monoxone or phosphoric acid in the step (3).
The present invention provides a kind of anionic gemini surfactant, the present invention using tartaric acid and fatty amine as raw material,
Raw material is easy to get, and synthesis technology is simple, at low cost, and tartaric acid Nantural non-toxic is degradable, and product uses discharge because containing amide group
After be readily biodegradable；
The present invention first synthesizes tartaric acid amide by tartaric acid and fatty amine, then passes through on two secondary alcohol of tartaric acid amide
Etherification reaction, substitution reaction or esterification etc. connect anionic group, and synthesis tartaric acid amide anion type Shuangzi surface is lived
Property agent, the Gemini surface active agent reduce aqueous solution surface tension ability be remarkably reinforced, critical micelle concentration value reduce by two
The order of magnitude, surface tension are 32mN/m or so, critical micelle concentration 10-5The order of magnitude.
Description of the drawings
Fig. 1 is change of tartaric acid amide anion type Gemini surface active agent TAS and TAC the aqueous solution surface tension with concentration
Change figure.
Specific implementation mode
The present invention provides a kind of anionic gemini surfactants, have structure shown in Formulas I：
N=5~29 in Formulas I, R are-SO3M、-CH2CH2CH2SO3M、-SO3OM、-COOM、-CH2COOM or-PO3M2, M is
Na+、K+Or NH4 +。
In the present invention, the n is preferably 5~19, and more preferably 7~17.
In the present invention, the anionic gemini surfactant preferably includes
The present invention provides upper
The preparation method for stating anionic gemini surfactant described in technical solution, includes the following steps：
(1) tartaric acid, thionyl chloride and solvent are mixed, carries out esterification, obtains diester tartaric acid used；
(2) the diester tartaric acid used, solvent and fatty amine are mixed, carries out amidation process, obtains tartaric acid amide；
(3) the tartaric acid amide is placed in reactor, under protective atmosphere, anion is added dropwise in ice-water bath
Change reagent, is reacted directly or under the action of catalyst, then with alkali neutralization, obtain tartaric acid amide anion type Shuangzi surface
Activating agent.
The present invention mixes tartaric acid, thionyl chloride and solvent, carries out esterification, obtains diester tartaric acid used.In this hair
In bright, the tartaric acid is preferably levotartaric acid.In the present invention, the solvent is preferably ethyl alcohol or methanol, it is furthermore preferred that
The ethyl alcohol is preferably absolute ethyl alcohol.In the present invention, the molar ratio of the thionyl chloride and tartaric acid is preferably 2~2.5, more
Preferably 2.2.
In the present invention, the mixing of the tartaric acid, thionyl chloride and solvent preferably mixes tartaric acid and solvent, so
Afterwards under agitation, thionyl chloride is added into gained mixture.In the present invention, the feed postition of the thionyl chloride is excellent
It is selected as being added dropwise；The present invention does not have the rate of the dropwise addition special restriction, is specifically such as added dropwise.
In the present invention, the temperature of the esterification is preferably the boiling point of solvent, and time of esterification is preferably 4~
16h, more preferably 6~12h.The present invention is preferably by way of oil bath heating by the mixing of tartaric acid, thionyl chloride and solvent
Object is heated to the temperature of the esterification；In an embodiment of the present invention, specifically it is heated to reflux.
After completing the esterification, the present invention preferably post-processes gained esterification material, obtains diester tartaric acid used.
In the present invention, the post-processing preferably includes following steps：
The solvent in the esterification material is removed, gained residue is extracted, gained organic phase is washed, is done
It is dry, obtain crude product；
The crude product is subjected to column chromatography for separation, the eluant, eluent in removal gained eluent obtains diester tartaric acid used.
The present invention does not have special restriction for method used by the solvent in the removal esterification material, using ability
Technical solution known to field technique personnel is specific as rotated.The present invention preferably mixes the residue with dichloromethane,
First extraction is carried out to gained mixture using saturated sodium bicarbonate solution, gained after then dichloromethane pair first being used to extract
Water phase carries out the second extraction, collects the first extraction and the second extraction gained organic phase carries out subsequent wash.Present invention preferably employs
Saturated salt solution washs extraction gained organic phase, and collects washing gained organic phase and subsequently dried.The present invention is excellent
Choosing is dried washing gained organic phase using anhydrous sodium sulfate, obtains crude product.
In the present invention, the eluant, eluent used during the column chromatography for separation is preferably the mixed of petroleum ether and ethyl acetate
Close object；The volume ratio of the eluant, eluent petrochina ether and acetic acid is preferably 1:(1.5~2.5), more preferably 1:2.The present invention couple
There is no special restriction in the method for removing the eluant, eluent, using technical solution well known to those skilled in the art, tool
Body is as rotated.
In the present invention, the reaction equation of the esterification is：
Obtain it is diester tartaric acid used after, the present invention mixes the diester tartaric acid used, solvent and fatty amine, and it is anti-to carry out amidation
It answers, obtains tartaric acid amide.In the present invention, the structural formula of the fatty amine is preferably H3C-(CH2)n-NH2, wherein n=5~
29.In the present invention, the solvent is preferably methanol or ethyl alcohol.
In the present invention, the mixing of the diester tartaric acid used, solvent and fatty amine is preferably by solvent and diester tartaric acid used
Mixing, then under agitation, fatty amine is added into gained mixture.In the present invention, the addition side of the fatty amine
Formula is preferably added dropwise；The present invention does not have the rate of the dropwise addition special restriction, is specifically such as added dropwise.
In the present invention, the temperature of the amidation process is preferably the reflux temperature of solvent, the amidation process
Time is preferably 6~12h, more preferably 8~10h.The present invention will be diester tartaric acid used, fatty preferably by way of oil bath heating
The mixture of amine and solvent is heated to the temperature of the amidation process；In an embodiment of the present invention, it is specifically heated to back
Stream.
After completing the amidation process, the present invention preferably post-processes gained amidation process material, obtains wine
Stone acid amide.In the present invention, the post-processing preferably includes following steps：
The amidation process material is cooled to room temperature, is washed and is recrystallized successively with absolute ethyl alcohol, obtain wine
Stone acid amide.
In the present invention, the reaction equation of the amidation process is：
After obtaining tartaric acid amide, the tartaric acid amide is placed in reactor by the present invention, under protective atmosphere, in ice
Anionic reagent is added dropwise in water-bath, is reacted directly or under the action of catalyst, then with alkali neutralization, obtains tartaric acid
Amide anion type Gemini surface active agent.In the present invention, the anionic reagent is preferably propane sultone, chlorine sulphur
Acid, monoxone or phosphoric acid.The catalyst is preferably sodium hydride or sodium, and alkali is preferably sodium hydroxide or potassium hydroxide.
In the present invention, the protective gas for providing the protective atmosphere is preferably nitrogen.
In the present invention, when the anionic reagent is propane sultone：
In the present invention, the mixing of the tartaric acid amide and anionic reagent preferably carries out under agitation.This
Invention does not have special restriction for the mode and rate of the stirring, using the technology of stirring well known to those skilled in the art
Scheme.After tartaric acid amide and anionic reagent are mixed, the present invention preferably in ice bath (0~10 DEG C), is stirring
Under the conditions of, catalyst is added in the mixture of tartaric acid amide and anionic reagent.Preferably catalysis is being added in the present invention
Tetrahydrofuran is added simultaneously during agent；In the present invention, the tetrahydrofuran is preferably anhydrous tetrahydro furan, the tetrahydrochysene
Furans is as reaction dissolvent.Catalyst is preferably averaged and is added in three times by the present invention so that catalyst fully reacts.The present invention is excellent
Choosing is slowly added to catalyst, overcomes highly exothermic caused by vigorous reaction.In the present invention, the feed postition of the catalyst is excellent
It is selected as being added dropwise.
In the present invention, the reaction temperature is preferably 10~35 DEG C, and more preferably 20~30 DEG C, the reaction time is excellent
It is selected as 24~60h.
After completing the reaction, the present invention preferably post-processes gained reactant material, obtain tartaric acid amide the moon from
Subtype Gemini surface active agent.In the present invention, the post-processing preferably includes following steps：
The catalyst and tetrahydrofuran in the reaction mass are removed, residue is dried, crude product is obtained；
The crude product is extracted, gained organic phase is dried, the extractant in resulting material is removed, will remain
Excess is washed and is dried, and tartaric acid amide anion type Gemini surface active agent is obtained.
After completing the reaction, the present invention preferably removes catalyst and tetrahydrofuran in the reaction mass, will be remaining
Object is dried, and crude product is obtained.The present invention does not have special limit for method used by the removal catalyst and tetrahydrofuran
It is fixed, using technical solution well known to those skilled in the art.Preferably ammonium chloride is added into the reaction mass in the present invention
Solution, to remove catalyst；In the present invention, the mass concentration of the ammonium chloride solution is preferably 10%.The present invention is preferably logical
Tetrahydrofuran is evaporated off in overwinding.The present invention does not have the temperature and time of the drying special restriction, using this field skill
Technical solution known to art personnel.
After obtaining the crude product, the crude product is preferably extracted, gained organic phase is dried by the present invention,
The extractant in resulting material is removed, residue is washed and dried, tartaric acid amide anion type Shuangzi surface is obtained
Activating agent.The present invention preferably mixes the crude product with ammonium chloride solution, then use n-butanol to gained mixed material into
Row extraction；In the present invention, the mass concentration of the ammonium chloride solution is preferably 10%.After completing the extraction, the present invention is excellent
Extraction gained organic phase is dried for choosing；Present invention preferably uses anhydrous magnesium sulfates to be dried the organic phase.It completes
After the drying, to removal, the method for extractant does not have special restriction to the present invention in resulting material after dry, using this field
Technical solution known to technical staff is specific as rotated.
Present invention preferably uses hot acetones to wash the residue.After completing the washing, the present invention preferably will
Resulting material is filtered, and obtained solid material is subsequently dried.In the present invention, the drying is preferred dry to perseverance
Weight.The present invention does not have special restriction to the filtering and dry mode, using mode well known to those skilled in the art into
Row filtering and drying.
When the anionic reagent is chlorosulfonic acid, tartaric acid amide is preferably dissolved in dichloromethane by the present invention, then will
The chlorosulfonic acid for being dissolved in dichloromethane is slowly dropped under ice bath in tartaric acid amide, the reaction was continued 6h, with the second of sodium hydroxide
Alcoholic solution neutralizes, and filtering rotates solvent, obtains crude product, then obtain white solid, i.e. tartaric acid amide with 95% ethyl alcohol recrystallization
Sodium sulfovinate.
When the anionic reagent is monoxone, the present invention preferably first mixes tartaric acid and catalyst and tetrahydrofuran
It closes, monoxone is then added.In the present invention, the monoxone is preferably added under conditions of 0~5 DEG C；It is described chloroacetic
Feed postition is preferably added dropwise, and is more preferably added dropwise.
It completes after monoxone is added dropwise, the present invention preferably continues stirring 2 hours at 0-5 DEG C.Present invention preferably employs liquid phases
The consumption process of chromatography raw material tartaric acid amide.After the completion of reaction, the preferred concentration of reaction solution of the present invention removes tetrahydrofuran,
Obtain tartaric acid amide carboxylic acid's sodium.
When the anionic reagent be phosphoric acid when, in the presence of triethylamine and tetrahydrofuran, by tartaric acid amide with
POCl330min is reacted at 0 DEG C, then hydrolysis dechlorination, finally use sodium ethoxide/alcohol treatment, obtain tartaric acid amidophosphoric acid ester sodium.
Anionic gemini surfactant provided by the invention is described in detail with reference to embodiment, still
They cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Absolute ethyl alcohol (70mL), ethyl tartrate (20.6g, 0.1mol) are mixed, are added dropwise under agitation
N-octyl amine (27.1g, 0.21mol), oil bath heating react 8h to flowing back.Wait for that reaction solution is completely cooled down to room temperature, with 150mL without
Water-ethanol washs three times, obtains white solid；Then needle-like white crystals are recrystallized to give to get to wine with 200mL absolute ethyl alcohols
Stone eight amides of acid, yield are (31.25g, 84.0%).
Eight amide of the tartaric acid (1.86g, 5mmol) and propane sultone (1.83g, 15mmol) are mixed, in nitrogen
60% sodium hydride (0.6g, 30mmol) and anhydrous tetrahydro furan (70mL) is added in atmosphere, in ice bath while stirring, wherein hydrogenating
Sodium is averagely added in three times, and 48h is reacted under room temperature, and after reaction terminates, it is extra that addition 10mL10% ammonium chloride solutions remove
Sodium hydride rotates and removes tetrahydrofuran, and drying to constant weight in vacuum drying oven obtains crude product.Crude product is dissolved in 20mL 10%
In ammonium chloride solution, 90mL extracting n-butyl alcohols are added three times, upper organic phase is taken to be dried with anhydrous magnesium sulfate, revolving obtains white
Solid is washed twice with 20mL hot acetones later, is dried to constant weight in vacuum drying oven after filtering, is obtained product.
Product structure characterizes：FTIR spectrograms：3330cm-1For N-H stretching vibration absorption bands；2850cm-1、2919cm-1For fat
Fat is saturated the stretching vibration absorption band of C-H；1645cm-1、1538cm-1、1466cm-1For the stretching vibration absorption band of N-C=O；
1130cm-1It is nearby C-O asymmetric stretching vibration absorption bands.
1H-NMR (400MHZ, DMSO, δ) ppm：0.85~0.88 (6H, t, CH3, 1)；1.26~1.30 (20H, m, CH2,
2-6)；1.41~1.45 (4H, tt, NH-CH2-CH2, 7)；3.08~3.12 (4H, m, NH-CH2, 8)；4.20 (2H, s, CH,
11)；5.14 (2H, s, OH, 10)；7.41~7.44 (2H, t, NH, 9)；2.49 (solvent peaks).
MS spectrograms：Quasi-molecular ion peak [M+1] is 373.3, so the molecular weight analyte of Mass Spectrometer Method is 372.3, with wine
The theoretical molecular weight 372 of stone eight amides of acid matches.What the present embodiment obtained is eight amidosulfonic acid sodium Shuangzi surface of tartaric acid
Activating agent (TAS-8).
Embodiment 2
Absolute ethyl alcohol (70mL) and ethyl tartrate (20.6g, 0.1mol) are mixed, are added dropwise under agitation
N-Decylamine (33.0g, 0.21mol)；Then oil bath heating reacts 8 hours to flowing back, waits for that reaction solution is completely cooled down to room temperature, uses
150mL absolute ethyl alcohols wash three times, obtain white solid；Then it is recrystallized to give ten amide of tartaric acid with 200mL absolute ethyl alcohols, produced
Rate is (35.57g, 83.1%).
Ten amide of the tartaric acid (1.86g, 5mmol) and propane sultone (1.83g, 15mmol) are mixed, in nitrogen
60% sodium hydride (0.6g, 30mmol) and anhydrous tetrahydro furan (70ml) is added in atmosphere, in ice bath while stirring, wherein hydrogenating
Sodium is averagely added in three times, and 48h is reacted under room temperature, and after reaction terminates, it is extra that addition 10% ammonium chloride solutions of 10mL remove
Sodium hydride rotates and removes tetrahydrofuran, and drying to constant weight in vacuum drying oven obtains crude product.Crude product is dissolved in 20mL 10%
In ammonium chloride solution, 90mL extracting n-butyl alcohols are added three times, upper organic phase is taken to be dried with anhydrous magnesium sulfate, revolving obtains white
Solid is washed twice with 20mL hot acetones later, is dried to constant weight in vacuum drying oven after filtering, is obtained white solid particle.
Product structure characterizes：FTIR spectrograms:3322cm-1For amide N-H stretching vibration absorption bands；2848cm-1、2916cm-1
For the stretching vibration absorption band of fat saturation C-H；1643cm-1、1541cm-1、1454cm-1It is absorbed for the stretching vibration of N-C=O
Band；1129cm-1It is nearby C-O asymmetric stretching vibration absorption bands.
1H-NMR (400MHZ, CDCl3, δ) and ppm：0.86~0.90 (6H, t, CH3, 1)；1.26~1.50 (32H, m, CH2,
2-9)；3.23~3.28 (4H, m, NH-CH2, 10)；4.25 (2H, s, CH, 12)；7.14 (2H, t, NH, 11)；7.26 (solvent
Peak).
MS spectrograms：Quasi-molecular ion peak [M-2H+1] is 427.3, so the molecular weight analyte of Mass Spectrometer Method is 428.3, with
The theoretical molecular weight 428 of ten amide of tartaric acid matches, and what the present embodiment obtained is ten amidosulfonic acid sodium Shuangzi table of tartaric acid
The synthesis (TAS-10) of face activating agent.
Embodiment 3
Absolute ethyl alcohol (70mL) and ethyl tartrate (20.6g, 0.1mol) are mixed, are added dropwise under agitation
Lauryl amine (38.9g, 0.21mol)；Then oil bath heating reacts 6-8h, waits for that reaction solution is completely cooled down to room temperature to flowing back, and uses
150mL absolute ethyl alcohols wash three times, obtain white solid；Then it is recrystallized to give tartaric acid lauramide with 200mL absolute ethyl alcohols,
Yield is (39.39g, 81.4%).
The tartaric acid lauramide (2.14g, 5nmol) and propane sultone (1.83g, 15mmol) are mixed, in nitrogen
60% sodium hydride (0.6g, 30mmol) and anhydrous tetrahydro furan (70mL), wherein hydrogen is added during atmosphere is enclosed, in ice bath while stirring
Change sodium to be averagely added in three times, 48h is reacted under room temperature, after reaction terminates, it is extra that the removing of 10% ammonium chloride solutions of 10mL is added
Sodium hydride, revolving remove tetrahydrofuran, drying to constant weight obtains crude product.It is molten that crude product is dissolved in 10% ammonium chlorides of 20mL
In liquid, 90mL extracting n-butyl alcohols being added three times, upper organic phase is taken to be dried with anhydrous magnesium sulfate, revolving obtains white solid, it
It is washed twice afterwards with 20mL hot acetones, is dried to constant weight after filtering, obtain white solid particle.
Product structure characterizes：FTIR：3327cm-1For amide N-H stretching vibration absorption bands；2848cm-1、2916cm-1For fat
Fat is saturated the stretching vibration absorption band of C-H；1644cm-1、1540cm-1、1466cm-1For the stretching vibration absorption band of N-C=O；
1129cm-1It is nearby C-O asymmetric stretching vibration absorption bands.
1H-NMR (400MHZ, CDCl3, δ) and ppm：0.87~0.90 (6H, t, CH3, 1)；1.27~1.29 (36H, m, CH2,
2-10)；1.47~1.52 (4H, tt, NH-CH2-CH2, 11)；3.22~3.26 (4H, m, NH-CH2, 12)；4.21~4.22
(2H, d, CH, 15)；5.31~5.32 (2H, d, OH, 14)；7.07 (2H, t, NH, 13)；7.25 (solvent peaks).
MS spectrograms：Quasi-molecular ion peak [M+1] is 485.4, so the molecular weight analyte of Mass Spectrometer Method is 484.4, with wine
The theoretical molecular weight 484 of stone acid lauramide matches, and what the present embodiment obtained is tartaric acid lauramide sodium sulfonate Shuangzi
Surfactant (TAS-12).
Embodiment 4
Absolute ethyl alcohol (70mL) and ethyl tartrate (20.6g, 0.1mol) are mixed, are added dropwise under agitation
Lauryl amine (38.9g, 0.21mol)；Then oil bath heating reacts 8h, waits for that reaction solution is completely cooled down to room temperature to flowing back, and uses
150mL absolute ethyl alcohols wash three times, obtain white solid；Then it is recrystallized to give tartaric acid lauramide with 200mL absolute ethyl alcohols,
Yield is (39.39g, 81.4%).
Sodium hydride (4.0 equivalent) and anhydrous tetrahydro furan are mixed；Under nitrogen protection, reaction temperature is adjusted to 0-5
DEG C, tartaric acid amide (1.0 equivalent) (remarks are slowly added dropwise：During dropwise addition, gas generation is had), said mixture is stirred
It mixes 2 hours；Under nitrogen protection, monoxone (2.05 equivalent) is slowly added dropwise, control temperature is in 0-5 DEG C of (remarks during being added dropwise：
During dropwise addition, gas generation is had)；After dripping monoxone, continue stirring 2 hours at 0-5 DEG C；Liquid-phase chromatographic analysis
Raw material tartaric acid amide completely consumes, reaction terminating；Concentration of reaction solution removes tetrahydrofuran to get tartaric acid lauramide carboxylic acid
Sodium TAC-12.
1H-NMR (400MHZ, D2O, δ) ppm：0.87~0.89 (6H, t, CH3)；1.26~1.31 (36H, m, CH2)；
1.48~1.52 (4H, t, NH-CH2-CH2)；3.20~3.24 (4H, m, NH-CH2)；4.32~4.33 (2H, d, CH)；4.31~
4.32 (2H, t, O-CH2)；8.04 (2H, t, NH)；4.82 (solvent peaks).
To the TAS-8 that Examples 1 to 4 obtains, TAS-10, TAC-12 are measured, and select lauryl sodium sulfate
(SDS) it is reference object, measurement result is shown in attached drawing.
By attached drawing 1 it is found that anionic gemini surfactant prepared by the present invention reduces the energy of aqueous solution surface tension
Power is significantly stronger than SDS surfactants.
As seen from the above embodiment, the present invention provides a kind of anionic gemini surfactant, the surfactants
It is middle because containing amide group, using being readily biodegradable after discharge；And the Gemini surface active agent reduces aqueous solution surface tension
Ability be remarkably reinforced, critical micelle concentration value can be down to 0.063mmol/L.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of anionic gemini surfactant has structure shown in Formulas I：
N=5~29 in Formulas I, R are-SO3M、-CH2CH2CH2SO3M、-SO3OM、-COOM、-CH2COOM or-PO3M2, M Na+、K+
Or NH4 +。
2. anionic gemini surfactant according to claim 1, which is characterized in that the anionic Shuangzi table
Face activating agent includes
Wherein n=5~29.
3. the preparation method of anionic gemini surfactant as claimed in claim 1 or 2, includes the following steps：
(1) tartaric acid, thionyl chloride and solvent are mixed, carries out esterification, obtains diester tartaric acid used；
(2) the diester tartaric acid used, solvent and fatty amine are mixed, carries out amidation process, obtains tartaric acid amide；
(3) the tartaric acid amide is placed in reactor, under protective atmosphere, anionic examination is added dropwise in ice-water bath
Agent is reacted directly or under the action of catalyst, then with alkali neutralization, obtains tartaric acid amide anion type Gemini surface active
Agent.
4. preparation method according to claim 3, which is characterized in that thionyl chloride and tartaric acid in the step (1)
Molar ratio is 2~2.5.
5. preparation method according to claim 3 or 4, which is characterized in that step (1) mesotartaric acid is left-handed winestone
Acid.
6. preparation method according to claim 3, which is characterized in that the solvent in the step (1) and step (2) is first
Alcohol or ethyl alcohol.
7. preparation method according to claim 6, which is characterized in that the temperature of esterification is molten in the step (1)
The time of the boiling point of agent, esterification is 4~16h.
8. preparation method according to claim 3, which is characterized in that catalyst in the step (3) be sodium hydride or
Sodium, alkali are sodium hydroxide or potassium hydroxide.
9. the preparation method according to claim 3 or 6, which is characterized in that the temperature of amidation process in the step (2)
Time for the reflux temperature of solvent, amidation process is 6~12h.
10. preparation method according to claim 3, which is characterized in that anionic reagent is the third sulphur in the step (3)
Acid lactone, chlorosulfonic acid, monoxone or phosphoric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810438784.4A CN108671849A (en) | 2018-05-09 | 2018-05-09 | A kind of anionic gemini surfactant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810438784.4A CN108671849A (en) | 2018-05-09 | 2018-05-09 | A kind of anionic gemini surfactant and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108671849A true CN108671849A (en) | 2018-10-19 |
Family
ID=63805972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810438784.4A Pending CN108671849A (en) | 2018-05-09 | 2018-05-09 | A kind of anionic gemini surfactant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108671849A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115594808A (en) * | 2022-10-31 | 2023-01-13 | 亚士防水科技（滁州）有限公司（Cn） | Bio-based anionic waterborne polyurethane and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11140485A (en) * | 1997-10-31 | 1999-05-25 | Lion Corp | Detergent composition |
| JP2001172669A (en) * | 1999-12-21 | 2001-06-26 | Lion Corp | Cleansing agent composition |
| DE102006014732A1 (en) * | 2006-03-30 | 2007-10-04 | Schneider, M., Prof. Dr. | New O-acylated citric, tartaric and malic anhydrides useful as intermediates |
| CN103623740A (en) * | 2013-10-23 | 2014-03-12 | 长江大学 | Gemini surfactant containing sulfo group and sulfate group anions |
-
2018
- 2018-05-09 CN CN201810438784.4A patent/CN108671849A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11140485A (en) * | 1997-10-31 | 1999-05-25 | Lion Corp | Detergent composition |
| JP2001172669A (en) * | 1999-12-21 | 2001-06-26 | Lion Corp | Cleansing agent composition |
| DE102006014732A1 (en) * | 2006-03-30 | 2007-10-04 | Schneider, M., Prof. Dr. | New O-acylated citric, tartaric and malic anhydrides useful as intermediates |
| CN103623740A (en) * | 2013-10-23 | 2014-03-12 | 长江大学 | Gemini surfactant containing sulfo group and sulfate group anions |
Non-Patent Citations (1)
| Title |
|---|
| 王辉等: "左旋酒石酸十二酰胺的合成", 《应用化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115594808A (en) * | 2022-10-31 | 2023-01-13 | 亚士防水科技（滁州）有限公司（Cn） | Bio-based anionic waterborne polyurethane and preparation method and application thereof |
| CN115594808B (en) * | 2022-10-31 | 2024-03-29 | 亚士防水科技(滁州)有限公司 | Bio-based anionic waterborne polyurethane and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101856600B (en) | Amphoteric ionic Gemini surfactant and synthetic method thereof | |
| CN112957998B (en) | Preparation method of surfactant composition | |
| CN103111229B (en) | Gemini type fluorocarbon surfactant containing sulfonic group and preparation method thereof | |
| ES2702807T3 (en) | Formulations of glyphosate based on compositions derived from natural oil metathesis | |
| CN101972612A (en) | Sugar-based quaternary ammonium salt gemini surfactant and synthesis method thereof | |
| CN102491922B (en) | Bishydroxyl sulfoacid betaine surface active agent and synthesis method thereof | |
| CN101538221A (en) | Preparation method of Oseltamivir phosphate | |
| CN107673987A (en) | Glucosyl group Shuangzi nonionic surfactant and its synthetic method | |
| CN102439219B (en) | Fabric softener and method for preparing same | |
| CN108671849A (en) | A kind of anionic gemini surfactant and preparation method thereof | |
| CN101372457A (en) | Preparation of alkyl trimethyl quaternary ammonium salt | |
| CN102321238A (en) | The preparation method of fatty amide Soxylat A 25-7 | |
| CN109020856B (en) | Thiocarbamide polyether-bridged chiral molecular tweezer and its preparation and application | |
| CN106699595B (en) | A kind of scheme for lacosamide preparation method | |
| CN114525180A (en) | Composition, preparation method and application | |
| CN101654419A (en) | Preparation method of fluvoxamine maleate | |
| CN101745341A (en) | Gemini surface active agent and preparation method thereof | |
| CN106946724B (en) | The synthetic method of monoamine base inhibitor class intermediate 2- acetylaminohydroxyphenylarsonic acid 2- benzyl malonic acid mono ethyl ester | |
| CN104741032A (en) | Method for preparing fatty acyl sodium methionine and composition comprising surfactant | |
| CN105566283B (en) | Chiral crown ether containing ent-Bayesian skeleton and preparation method and application thereof | |
| CN106831491A (en) | The preparation method of 2 (2 (2 amino ethoxy) ethyoxyl) ethylcarbamates | |
| CN106946740B (en) | A method of preparing Crebinostat intermediate 7- diazanyl-N- hydroxyl -7- oxo heptamide | |
| CN109293569A (en) | A method of the amine reaction that turns that no catalyst participates in prepares carboxamides derivatives | |
| EP2896642A1 (en) | Method for producing polyalkylene glycol derivative with narrow molecular weight distribution, and acetal-group containing alcohol compound for use therein and alkali metal salt thereof | |
| CN115819266B (en) | Gemini type surfactant and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181019 |